Stereospecificity and Stereoselectivity

Definitions from Stereochemistry of Organic Compounds (Eilel):

Stereoselectivity
• The preferential formation of one stereoisomer over another in a chemical reaction. If the stereoisomers
are enantiomers, one speaks of enantioselectivity (quantified by ee); if they are diastereomers, one speaks
of diastereoselectivity.

Stereospecific
• A reaction is termed stereospecific if, in such a reaction, starting materials differ only in their configuration
are converted to stereoisomerically distinct products. According to this definition, a stereospecific process
is necessarily stereoselective, but stereoselectivity does not necessarily imply stereospecificity.

• The term may be extended to a process involving a chiral catalyst, enzyme, or reagent when the
configuration of the product of the reaction depends uniquely on the configuration of the catalyst or
reagent., i.e. becomes reversed when a catalyst or reagent of opposite configuration is employed.

Definitions from Modern Physical Organic Chemistry (Anslyn and Dougherty):

Stereoselectivity
• A stereoselective reaction is one in which a single reactant can give two or more stereoisomeric
products, and one or more of these products is preferred over the others – even if the preference is
very small.

Stereospecific
• In a stereospecific reaction, one stereoisomer of the reactant gives one stereoisomer of the product,
while a different stereoisomer of the reactant gives a different stereoisomer of the product.

Steps:
1. Look at your reaction.
2. If multiple stereoisomeric products are possible, but one is produced in excess, the reaction is
stereoselective.
3. Consider the stereochemical features of the reactants to determine stereospecificity or lack thereof.
o If another stereoisomer of the reactant will give identical products in identical ratios, then the
reaction is not stereospecific.
o If a different stereoisomer of the reactant or reagent gives a stereoisomerically different product,
then the reaction is stereospecific.
A Somewhat Tricky Example:

Angew. Chem. Int. Ed. 2008, 47, 10106

tBu tBu
OTMS Reaction is
OAc O O stereoselective
tBu because one
tBu tBu + tBu stereoisomer is
Bi(OTf)3 produced in excess
Ph MeNO2, RT Ph Ph (diastereoselective)
92% 8%

You may be tempted to say it is also stereospecific because if another stereoisomer of the starting
material were used, the reaction would give different stereoisomeric products.

tBu tBu
OTMS
OAc O O
tBu
tBu tBu + tBu
Bi(OTf)3
Ph MeNO2, RT Ph Ph

But, because there is a stereoisomer of of the original molecule that gives identical products in an
“identical” ratio, the reaction is not stereospecific.

tBu tBu
OTMS
OAc O O
tBu
tBu tBu + tBu
Bi(OTf)3
Ph MeNO2, RT Ph Ph
96% 4%